Science and Technology of Energetic Materials

Vol.61, No.3 (2000)

Research paper

The exothermal decomposition of nitrocellulose in mixed acids
Hidetsugu Nakamura, Noriaki Matsuura, Miyako Akiyoshi, 
and Yasutake Hara


The exothermic decomposition of nitrocellulose in a solution of mixed acid was studied in order to determine the conditions for safe production of nitrocellulose by means of the nitration of cellulose with mixtures of nitric acid and sulphuric acid. Isothermal decomposition tests were carried out and a temperature slightly higher than the nitration temperature in manufacturing was adopted as an experimental condition. The results obtained are as follows.
  Nitrocellulose in mixed acid underwent exothermic degradation after a long induction period, which was affected by the reaction temperature. This degradation showed the maximum rate in the middle of the reaction, which indicated the reaction to be autocatalytic. The activation energies obtained by Arrhenius plots of rate constants from the autocatalytic rate equation were 31.4 - 59.1 kJ/mol . Moreover, plots of the logarithm of the induction period t vs. the inverse of reaction temperature also showed good linearity according to the Arrhenius-type equation, and the obtained activation enrgies were 37.3 - 60.4 kJ/mol .
  The induction period after which the exothermic reaction commenced decreased with the increasing NC/mixed acids ratio. An increase in the content of nitric acid in the mixed acid then had a decreasing effect on the induction period. Moreover, this degradation was affected by atmospheric gases, and nitrogen dioxide accelerated the reaction.

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